JP3207026B2 - Diacrylic cyclic phosphate monomer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel diacrylate cyclic phosphate monomer and a method for producing the same.

The novel diacrylic cyclic phosphate monomer referred to in the present invention is a diacrylic cyclic phosphate monomer having a property of being at least dispersible or soluble in an oily solvent such as a toluene solvent. Has the property of imparting rubber elasticity to the polymer compound.

[0003] Polyhydric acrylic ester monomers are extremely rich in photopolymerization reactivity. The polyhydric acrylic ester monomer exhibits excellent reactivity at the time of polymer formation, and at the time of polymerization with other substances and other polymer formation.

[0004] The diacrylic cyclic phosphate monomer is
Due to the molecular structure characteristic of diacryl, it is rich in reactivity as in the above example. Moreover, since it is an oil-soluble substance, it has good compatibility with various substances and can be easily used as a modifier, and has a wide range of uses and usefulness in photosensitive resins and related fields.

A photosensitive resin using a polyvalent acrylic ester monomer has a disadvantage that it is hard and brittle, but it is possible to make up for this disadvantage by adding a phosphate ester monomer having a diacrylic cyclic structure. . Also, it exerts a positive modifying effect on improving the adhesiveness to the photosensitive resin and imparting rustproofness to the metal.

[0006]

2. Description of the Related Art Diacrylate phosphate monomers which do not have a cyclic structure even though a phosphate group and an amine group are interposed in the molecular structure exist in both known examples and known examples. However, a conventional example of a diacrylic phosphate monomer having a cyclic structure in which a phosphate group and an amine group are interposed in the molecular structure cannot be found.

[0007] A number of patent applications utilizing a conventionally known acid phosphate ester monomer such as acid phosphoethyl methacrylate copolymerized with various vinyl monomers and utilizing the copolymer have been published in patent publications to date. Hundred cases are counted.

[0008] As described above, there are the following techniques for producing new monomers which are used on the other side.

As an invention similar to the present invention, an acrylic acid phosphoric acid ester monomer (acid phosphoethyl acrylic ester) outside the scope of the present invention is obtained in an anhydrous state different from the present invention and in the presence of a polymerization inhibitor. The production method of reacting amines (aminoethyl methacrylates) is specified in JP-A-57-197250. As an example of application of a general monomer production technique, as shown in JP-A-58-21688, while preventing a polymerization side reaction of an acryl group in the presence of a polymerization inhibitor such as MEHQ, a solvent in a solvent is used. And a method of performing solvent extraction and purification.

[0010]

[Problems to be Solved] Among the published patent application examples, in the case where an acidic phosphate ester is used for solution polymerization, when the amount of the acidic phosphate ester used is increased due to the strong associative property of the phosphate group, it is difficult to increase the amount of the acidic phosphate ester used. Since the polymerized resin gels in the solution, it is often necessary to keep the weight ratio of the acidic phosphoric acid ester monomer in the monomer used to several percent or less.

Specific examples include isopropanol,
In many cases, the ratio of the acrylic acid phosphoric acid ester monomer to all the monomers used in a polar solvent such as methanol, butyl cellosolve, or ethyl acetate is mainly about 5% to about 1% by weight. A known example is disclosed in
3-77292, JP-A-57-53571, JP-A-57-53571
-77293, JP-A-53-19348, JP-A-53-18638, JP-A-54-36338, JP-A-57-1
90060, JP-A-58-47071, JP-A-58-4
7070, JP-A-48-79835 and the like, and JP-B-49-14330 and JP-B-48-4 of the inventor's earlier invention.
4675 also belongs to this.

In the case where the solvent for the solution polymerization is a non-polar solvent such as benzene, toluene and xylene, see JP-A-56-1.
27671, JP-A-52-25829, JP-A-53-232
The ratio of the acrylic acidic phosphate monomer used in Examples 6874 and JP-A-49-118499 to all the monomers used is mainly from about 0.1% to at most about 0.5% by weight. .

[0013] The reason why the ratio of use is so small is that the acrylic acid phosphate monomer in the above-mentioned known examples does not dissolve in non-polar solvents such as benzene, toluene and xylene. Toluene is now very commonly used in solvent-based paints, but in order to increase the proportion of acrylic acid phosphate monomer used and increase the desired modification effect, at least disperse it in toluene. Or have to be dissolved.

In order to prepare an acrylic acid phosphoric acid ester monomer which can be dispersed or dissolved in toluene, various kinds of acrylic acid phosphoric acid are disclosed in Japanese Patent Application Laid-Open No. 57-197250, which is a reaction example most similar to the present invention. As a result of experimenting the reaction of an acrylic monomer salt having an amine group of an ester monomer, one of the compounds has an 'amine group of an acrylic acid phosphate monomer which does not disperse or dissolve in toluene. Acrylic monomer's salts are generated, and in some cases, by-products of polymerization of acrylic groups are generated during the above-mentioned acid-base reaction. Therefore, the reaction according to JP-A-57-197250 could not be a means for solving the above-mentioned problem.

As one measure to solve this problem, Japanese Patent Application Laid-Open No. Sho 58-2, which is an example in which a general monomer production technique is applied.
According to 1688, an acid-base reaction between an acrylic acid phosphate monomer and an acrylic monomer having an amine group was attempted using a large amount of a polymerization inhibitor such as MEHQ. The reaction could not be prevented.

In view of the above problems, the present invention provides a diacrylic resin which is highly reactive to a photosensitive resin using a polyvalent acrylic ester monomer, imparts rubber elasticity thereto, and is dispersed or dissolved in an oily solvent such as toluene. An object of the present invention is to provide a method for producing a cyclic phosphate ester monomer by suppressing a polymerization side reaction and selectively proceeding an acid-base reaction while providing a cyclic phosphate ester monomer.

[0017]

According to the above-mentioned JP-A-57-197250, the inventors of the present invention disclosed a salt of an "acrylic monomer having an amine group" of various types of acrylic acid phosphate monomers. As a result of experimenting on the reaction, it could not be a means to solve the above problem, but the reaction system has an acrylic acid phosphate ester monomer 'amine group in the presence of a small amount of water in the liquid phase. The discovery that an oil-soluble polymer of an acrylic monomer salt has been generated, and that the polymerization of the acrylic group can be inhibited by slowly proceeding the acid-base reaction in the presence of a considerable amount of water. Also found.

Using these two findings, the general formula

Embedded image (Wherein R ₁ is an H or CH ₃ group, n is an integer of 3 or more and 8 or less) and an acrylic monomer having an amine group in the presence of water. A series of reaction processes for reacting the monomers to produce a diacrylic cyclic phosphate monomer is defined as a method for producing a diacrylic cyclic phosphate monomer, and is a means for solving the above-mentioned problems.

The above-mentioned water is present in such a manner that water in the liquid phase is interposed in the whole reaction system, and the reaction solution is stirred to suppress the polymerization reaction in the reaction system. This allows the acid-base reaction between the acrylic acid phosphate monomer, which is an acidic substance, and the acrylic monomer having an amine group, which is a basic substance, to proceed slowly and selectively.

The acrylic acid phosphate monomer used in the present invention is represented by the following general formula:

Embedded image (Wherein R ₁ is an H or CH ₃ group, and n is an integer of 3 or more and 8 or less).

Of the acrylic acid phosphate monomers used in the present invention in the above general formula, a few typical examples are specifically shown. Acid phosphooxytrioxypropylene glycol monomethacrylate, acid phosphooxy Trioxypropylene glycol monoacrylate, acid phosphooxytetraoxypropylene glycol monomethacrylate, acid phosphooxytetraoxypropylene glycol monoacrylate, acid phosphooxypentaoxypropylene glycol monomethacrylate, acid phosphooxypentaoxypropylene glycol monoacrylate, acid phosphooxy Hexaoxypropylene glycol monomethacrylate, acid phosphooxyhexaoxypropylene glycol mono Acrylic acid phosphate esters such as acrylate, acid phosphooxyheptaoxypropylene glycol monomethacrylate, acid phosphooxyheptaoxypropylene glycol monoacrylate, acid phosphooxyoctaoxypropylene glycol monomethacrylate, and acid phosphooxyoctaoxypropylene glycol monoacrylate Is a monomer.

Specific examples of the acrylic monomers having an amine group used in the present invention include aminoethyl methacrylate, aminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, and diethylaminoethyl. Acrylic monomer having an amine group such as acrylate.

[0023]

The inventors of the present invention have reported the mechanism of action of phosphate groups at the 35th Polymer Research Conference (Kobe 1989) entitled "Structure and Properties of Polymer Gels Containing Phosphate Groups". I have. According to the research report, "Acid phosphoethyl methacrylate and 2-hydroxyethyl methacrylate copolymers are almost completely crosslinked when acid phosphoethyl methacrylate is used in a small amount of up to 6 mol% based on all monomers used in the copolymerization. No structure is shown, but 6 mol%
For the above high concentration, the crosslink density increases in proportion to the concentration. "

The present inventors have paid attention to the possibility of dissolving toluene as a means for verifying the above-mentioned crosslinking phenomenon, and as a result of repeating various experiments, it has been found that even a homopolymer has a gelled structure in molecular structure, that is, toluene which does not have a crosslinked structure. It has been found that soluble acrylic phosphate monomers can be produced.

For example, acid phosphooxypolyoxypropylene glycol monomethacrylate having an average molecular weight of 440 (n = about 5 in the acrylic acid phosphate monomer represented by the above general formula.
Is a viscous liquid substance. The phosmer PP having an average molecular weight of about 1 mol, which is an acidic substance, is added to a reaction temperature of 60.
At ８０80 ° C., 1 mole of a basic substance, for example, an acrylic monomer dimethylaminoethyl methacrylate having an amine group, is added in the presence of 1 to 15% by weight of water of the whole reaction composition in the presence of water. When acted upon, the phosmer PP dimethylaminoethyl methacrylate half salt is produced.

The product obtained by subjecting the thus obtained dimethylaminoethyl methacrylate half salt, which is a diacrylic cyclic phosphate monomer, to a dehydration treatment step is as follows:
Dissolve or disperse in toluene. This is a special effect of the amines discovered by chance. The homopolymer of the phosmer PP dimethylaminoethyl methacrylate half salt is also soluble in toluene and does not form a crosslinked structure in molecular structure.

Needless to say, the acrylic monomers having an amine group used in the above-mentioned production method are not limited to the above-mentioned dimethylaminoethyl methacrylate. The verification of the presence or absence of a cyclic structure in the molecular structure of the monomer is determined by the form of the polymer obtained by the polymerization reaction. That is, if the polymer is dissolved in a solvent, it becomes a proof of a cyclically linked fibrous polymer, so that the polymer is determined to have a cyclic structure in terms of molecular structure. On the other hand, a polymer having a crosslinked structure is generally insoluble in a solvent, and is determined not to have a cyclic structure like a conventional polyvalent acrylic ester.

The thread polymer of the diacrylic cyclic phosphate monomer according to the present invention is represented by the following general formula having a cyclic connection structure.

[0029]

Embedded image (N is an integer of 3 or more and 8 or less; R ₁ is an H or CH ₃ group;
₂ is H or CH ₃ group, R ₃ is H or CH ₃ group or C ₂
In H ₅ group) provided that the general formula representing the polymeric state, when n = 1, as described above, shows the physical properties as if showing a crosslinked structure, 2 when n = 2 is such as to have an incomplete ring structure It has been experimentally shown that the material exhibits physical properties and, when n = 10 or more, tends to have an incomplete cyclic structure.

For example, in the general formula of the above-mentioned acrylic acid phosphate monomer, the reaction proceeded in exactly the same manner as described above for the example of acid phosphopropyl methacrylate as an example where n = 1, but the reaction proceeded smoothly. , Generated 'acrylic monomer having an amine group' half salt,
That is, the acid phosphopropyl methacrylate 'amine group-containing acrylic monomer' half salt was insoluble in toluene, and the respective homopolymers were insoluble in toluene.

[0031]

EXAMPLES Examples and results of verification based on the dissolution of toluene will now be described in detail with reference to the tables. The number of parts shown in the following Table 1 indicates a reaction weight ratio or a mixing weight ratio.

[0032]

The acrylic acid phosphate ester monomer and water in the number of parts shown in Table 1 are put into a flask equipped with a stirrer and a temperature controller, and the stirring is continued. Then, when the number of parts of the acrylic monomer having an amine group shown in Table 1 is dropped into a mixture of the acrylic acid phosphate monomer and water being stirred, the reaction liquid causes an exothermic reaction. The exothermic reaction solution is adjusted to 60 ° C. by a temperature controller, and the dropping of the acrylic monomer having an amine group is performed over 5 minutes. After completion of the dropwise addition, the temperature of the reaction solution is raised to 80 ° C., and stirring is continued for 1 hour. The “acrylic monomers having an amine group” half salt itself thus produced are only a few examples of the diacrylic cyclic phosphate monomer of the present invention.

However, these substances are hydrated substances,
This moisture interferes with the toluene verification. It is necessary to remove water, which is a disturbing factor, from these substances for verification. To remove such water, 7
Drying air is passed through the inside and outside of 0 ° C., and the drying is completed when the water content of the whole reaction solution becomes 2% by weight or less.

In the reference example, the above reaction is carried out in exactly the same manner as in the example to obtain a half salt of an acrylic monomer having an amine group of an acidic phosphate ester monomer. The same applies to the dehydration procedure for verification.

The monomers of Examples and Reference Examples synthesized according to the above procedure are dissolved in an equal amount of toluene, and the solubility in toluene is determined.

The physical properties of the thermally polymerized homopolymer in a test tube are observed.

A solution of about 75% of the product monomer and 25% of the solvent is thermally polymerized in a test tube, and after the generation of a polymer is confirmed by viscosity increase or the like, toluene is added, and the solubility in toluene is checked.
These test results are as shown in Table-2.

[0038]

[Table-2] According to the above test result table, a diacrylic cyclic phosphate monomer was completed limited to the scope of the present invention, and the polymer of the monomer of the present invention did not take a gelled structure in molecular structure, but a cyclic linked polymer structure. Has been demonstrated.

[0039]

As described in detail above, according to the method for producing a diacrylic cyclic phosphate monomer of the present invention, it has a wide range of usefulness in the chemical industry, especially in the field of photosensitive resins. A novel diacrylic cyclic phosphate monomer having the property of being soluble in an oleaginous solvent can be produced without generating an acrylic group polymerization by-product during the acid-base reaction.

[Table 1]

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Shozo Yanagita 2-10-13 Uguidai, Kawanishi-shi, Hyogo (56) References JP-A-63-199711 (JP, A) (58) Fields investigated (Int. Cl. ^7, DB name) C07F 9/09 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound of the general formula (N is an integer of 3 or more and 8 or less; R ₁ is an H or CH ₃ group;
₂ is H or CH ₃ group, R ₃ is H or CH ₃ group or C ₂
A diacrylate cyclic phosphate monomer having a cyclic structure formed by an associated acrylic group represented by the formula (H ₅ group) and an acid-base bond. 2. A compound of the general formula (Wherein R ₁ is an H or CH ₃ group, and n is an integer of 3 or more and 8 or less), in the presence of water, an acrylic acid phosphate monomer represented by the general formula: Wherein R ₂ is an H or CH ₃ group, and R ₃ is an H or CH ₃ group or a C ₂ H ₅ group. Item 3. The method for producing a diacrylic cyclic phosphate monomer according to Item 1. 3. The diacrylic cyclic phosphate ester monomer according to claim 1, wherein water in the liquid phase is interposed in the whole reaction system, and the acid-base reaction is selectively progressed slowly while stirring the reaction solution. How to make the body.